Stable petroleum distillate fuels containing nu-substituted aminopropylamine salts of 2, 4-dinapthenyl-3-thiaglutaric acids



United States Patent No. 770,948 r 'Claims. (CI. 44-71) This invention relates to stable liquid petroleum distillate fuels. More particularly, the invention is concerned with the stabilization of liquid petroleum distillate fuels tending toward instability during storage by incorporation therein of new salt compositions.

Liquid petroleum distillate fuels often exhibit a tendency toward instability during storage at ordinary atmospheric temperatures. For example, straight run distillate fuel oils can form sludge during storage despite their high content of normally stable paraffinie hydrocarbons. Where sludge deposition occurs in such oils, it is usually attributed to the presence in the oils of materials that are not normally present, e.g., impurities picked up during refining, or perhaps remaining in the oil due to incomplete refining, rather than to the inherent instability'of the oil itself. Sludge formation in straight run fuel oils is considered to be chiefly a problem of oxidation and the formation of insoluble oxygenate products. a

Unlike straight run distillate fuel oils, catalytically cracked fuel oil distillates are rich in olefinic, aromatic and mixed olefinic-aromatic components. Sludging in the latter oils is considered to involve primarily condensation and/or polymerization type reactions which result in the formation of insoluble reaction products of relatively high molecular weight.

Distillate fuel oil compositions containing mixed straight run and catalytically cracked fuel oil distillates have proved especially troublesome with regard to sludge deposition during storage at normal atmospheric temperatures. It has been found that the sluding characteristics of such mixed, or blended, fuel oil distillates are strikingly poor, much poorer than can be accounted for from the known sludging characteristics of the individual component fuel oil distillates alone. While the sludge formed in mixed distillate fuel oils no doubt contains some sludge of the type formed in each component oil, the sludge formed in the blended fuel oils is consistently greatly in exces of the amount that can be accounted for from the known sludging tendencies of the individual component oils, thus'indicating the existence of a special problem.

On the other hand, gasolines tend to form gum during storage. In contrast to fuel oil sludge, which is recognized as an insoluble precipitate in the fuel oil, the gums formed in gasoline are soluble thereinand do not appear as such except upon evaporation of the gasoline. The problem of gum formation is considered to involve primarily the oxidation of reactive olefinic linkages.

We have found that the storage stability of liquid;

petroleum distillate fuels can be substantially improved by incorporation therein of small amounts .of the multifunctional salt compositions disclosed herein. Ihe compounds whose use is included bythis invention are the salts of 2,4-dinaphthenyl-3-thiaglutaric acids and 1,3

where R is an aliphatic radical containing from 8 'to30 carbon atoms,

The salts whose use is included by this invention'are prepared by neutralization of 2,4-dinaphthenyl-3- thiaglutaric acid with a 1,3-diaminopropane that contains a long-chain, aliphatic radical-substituted, secondary amino grouping. The aforesaid neutralization reaction normally takes place spontaneously at room temperature T with evolution of heat, but in some cases moderate heating may be desirable in order to accelerate the reaction. a In no case should the reaction be carried out at temperatures in excess of about F., since decomposition of a the resulting ammonium salt may occur with prolonged exposure to temperatures substantially in excess of this limit. Depending upon whether the desired salt is a substantially neutral diammonium salt, or a diamino-diam-' monium salt, the mol ratio of the acid to diamine may vary between about 1:1 and about 1:2.

The diaminopropanes that form salts whose use is included by this invention may be illustrated by the generic formula:

where R is an aliphatic radical containing from 8 to 30 propylamine, 3-docosylaminopropylamine, 3-docosenyl aminopropylamine, 3 docosodienylaminopropylamine, and 3-triacontanylaminopropylamine. Within the general class of 1,3-diaminopropanes capable of forming the salts of this invention, the diamines in which the longchain, aliphatic N-substituent of the secondary amino grouping is an alkyl or alkenyl group containing at least 12 and preferably from 12 to 18 carbon atoms are considered to form especially eifective addition agents. Ex-

amples of 1,3-diaminopropanes which are considered to form especially efiective 2,4-dinaphthenyl-3-thiagultarates for the purposes of this invention are the 3-dodecyl-', 3

hexadecylarninopropylamines, and especially the 18 carbon alkyl-, alkenyl-, and alkadienyl-substituted -l,3-

3-octa-- diaminopropanes, such as the 3-octadecyl-, decenyl-, and 3-octadecadienylaminopropylamines. Al-

though aliphatic hydrocarbon N-substituted 1,3-diamind-i propanes are preferred, the invention also includes salts.

derived from diamines in 'which the N-substituent of the secondary amino grouping is itself substituted with one or more groups that contain elements such as oxygen; sulfur, nitrogen or halogens and that do not interfere Representative ex-' with the oil-solubility of the salt. amples of 1,3-diaminopropanes containing such substituents are 3 ricinoleylaminopropylamine and 3-(chlorostearyl)aminopropylamine. Mixtures of 1,3-diaminopropanes such as are formed when the long-chain, aliphatic N-substituent in the secondary amino grouping is derived from mixed fatty acids obtained from naturally occurring fats and oils form highly effective 2,4-dinaphthenyl-3-" thiaglutarates within the scope of this invention. such instances the aliphatic N-substituent in the secondary amino grouping will be a straight-chain monovalent hydrocarbon radical containing from 8 to 20 carbon atoms. Examples of such mixtures of 1,3-diaminopro- I panes are 3-tallow-aminopropylamine, 3--soya-amino- Patented June 27, 1961 3 propylamine, and 3-coco-aminopropylamine where the respective N-substituents are mixed alkyl and unsaturated alkyl groups derived from animal tallow (C -C fatty acids, soybean (C -C fatty acid, an coconut (C -C fatty acids.

The 2,4-dinaphthenyl-3-thiaglutaric acids from which are formed the addition salts disclosed herein are. acids containing an alicyclic hydrocarbon grouping attached to a 3-thiaglutaric acid residue:

CCOOH where x is a number from 1 to 2, whether the alicyclic grouping is attached to the 2 and 4 carbon atoms, or whether the 2 and 4 carbon atoms themselves are part of the'st-ructure forming an alicyclic link. Since alicyclic or cycloaliphatic hydrocarbons are conventionally called naphthenes, the term naphthenyl is used herein and in the appended claims to' denote the alicyclic substituents of the 3-thiaglutaric acids.

The 2,4-dinaphthenyl-3-thiaglutaric acids can be prepared in any suitable way, for example, by the method disclosed in copending application Serial No.'449,492, filed August 12, 1954, in the names of Fareri and Pellegrini, of which this is a division. Although for this reason it is considered unnecessary to describe the preparation of these acids in detail, in the interest of clarity it may be briefly mentioned that such acids .can be made by halogenating a naphthenic acid containing a secondary or .tertiary carbon atom in the alpha position to the carboxylic. acid group and reacting thealpha-halonaphthenic acid thus obtained with an alkali "metal monosulfide, (ii-sulfide or mixtures thereof to form a 2,4- dinaphthenyl-3-thiaglutaric acid. H

The 2,4-dinaphthenyl-3-thiaglutaric acids capable of forming the salts disclosed herein include those derived from the well-known petroleum naphthenic acids. As is well-known in the art, the petroleum naphthjenic acids are obtained by caustic soda extraction of naphtha, kerosene, gas oil and lubricating distillates. Conventional petroleum naphthenic acids contain from about 7 to 30 carbon atoms andpossess an average molecular weight ranging from about 200 to about 450. Although 2,4- dinaphthenyl-3-thiaglutaric acids that have been; derived from petroleum naphthenic acids are preferred because of their relatively low cost, our invention is not limited thereto. The invention also includes the use of salts of 2,4-dinaphthenyl-3-thiaglutaric acids derived from synthetic naphthenic acids such as cyclopentylacetic acid, 2,2,3-trimethylcyclopentylacetic acid, hexahydrobenzoic acid (cyclohexane carboxylic acid), cyclohexylacetic acid, 3-methylcyclohexylacetic acid, cyclohexylpropionic acid, cyclohexylstearic acid and corresponding 'alkyl cyclohexyl or dicyclohexyl fatty acids.

As indicated, the reaction products of the abovedescribed neutralization of the 2,4-dinaphthenyl-3-thiaglutaric acid with the long-chain, aliphatic N-substituted 1,3-diaminopropanes vary from the substantiallyn'eutral diammonium salts to salts of the diaminodiammonium type, depending upon whether the acidzdiamine ratio in the neutralization reaction is 1:1 or 1:2. In the former instance'the substantially neutral diammonium'salts are considered to have the following probable generic formula:

where R is a naphthenyl or alicyclic hydrocarbon substituent and R is as defined above. In the latter instance the diamino-diammonium salts are considered to have the following probable generic formula:

where R and R are as defined above. The term su stantially neutral is employed to describe salts. in which substantially no unneutralized carboxyl or amino groups are present.

As indicated, the salt compositions disclosed. herein have been found effective in small concentrations,- to alleviate problems of storage instability of liquid petroleum distillate fuels. For example, the salts of this invention effect a marked improvement in the storage stability of petroleum distillate fuels boiling in the gasoline range, especially cracked gasolines, which are particularly troublesome with regard to lgum formation. The salts of this invention are also useful as sludge inhibitors in distillate fuel oils such as are used. for domestic heating and for heating purposes in some industrial processes, typical of which are the so-called No. 2 fuel oils, i.e., distillate oils "boiling within the: approximate range of 350 to 750 F. and having a minimum API gravity of about 26. The salts of this invention are especially valuable for inhibiting sludgedeposition in mixtures of straight run and catalytically cracked distillate fuel oils, which oils, as indicated above, are especially troublesomefiThe problem ofsludging-in mixed distillate fuel oils is serious when the volume-ratio.

of the catalytically crackedand straight runoil is between'a'bout 9:1 and 1:9. The problem is particularly troublesome when the ratio is within the range of .about.

of the distillate fuel to be inhibited. In general, however, the herein disclosed salts are useful in concentrations of as litle as about 0.005 percent to about 1.0 'p'ercent by weight of the composition. Major improvement of-the storage stability characteristics of gasolines and distillate fuel oils is usually obtainable by incorporation therein respectively of from about 0.01 toabout -0.5 weight percent, and from about 0.01 to-about 0.05 percent by weight of the hereindisclosed class ofsalts. In

some cases involving fuel oils it will be advantageous to. add as much as about 0.1 percent by weight of the in hibitor, and in unusual instances involving either-.distillate fuel it may be found desirable to add, as much as about 1.0 percent by weight of the inhibitor.

The 2,4-dinaphthenyl-3-thiaglutarates whose use is included by this invention may be incorporated in the liquid distillate fuels in anysuitable manner. Thus, the saltsmay be formed in situ in the fuel, they may be added, per se, directly to the fuel, or they maybe added in the form of concentrates, either immediately after distillation and/or blending of the distillate fuels, or,

as in the case of fuel oils, after the fuel has been stored for a substantial period of time. Inthe eased blended fuels, such asmixed catalytically cracked andfstraig ht run distillate '-fuel oils,tl1'e s'alts offthisinvention 'rriayfbe 166D centrated solutions or dispersionstfe'itlieftli formed in situ: in, 'or' addediper sear intlief "sta t sa t r m k tf e i s l ate i rt blending of thesegcomponents to form a fuel oil. Regardless of the .;nature of the fuelto be inhibited, it is generally preferred to employ preformed salts, usually in the form of concentrates, in the blending procedure. Suitable concentrates containing'the' addition agents disclosedherein comprise, for'exaniple,i"mineral oil solu-' tions or dispersions containing from about to 75 weight percent, and preferablyfrom about 25 to 50 weight percent active ingredient. Where the concentrates are in the form of dispersions itmay be desired to heat the concentrates and/or the fuel,,e.g., in the case of a fuel oil to about 100 to 140 F., in order to facilitate blending. An alternate blending procedure involves the incorporation in thefuel 'at storage temperature of concentrated solutions of the inhibitors in solvents, other than mineral oils, that have a high degree of solubility for the inhibitors and that do not" adversely -alfect the stability or other characteristics of the fuel. Examples of such concentrates are 10 to 75 weight percent, e.g., 50 weight percent, solutions of the substantially neutral salts and the diamino-diammonium salts of 3-tallowaminopropylamine and 2,4-dinaphthenyl-3-thiaglutaric acid in solvents such as benzene, toluene, hexane, methyl isobutyl ketone andmethylethyl ketone.

The utility of the herein disclosed [class of 2,4-dinaphthenyl-3-thiaglutarates has been demonstrated by subjecting liquid petroleum distillate fuels containing small concentrations of the same to standard stability tests. For example, mixtures of catalytically cracked and straight nun fuel oil distillates containing minute amounts of representative salts of the class included by the invention have been subjected to -a standard accelerated stability test. These test samples were made up by adding the desired concentration of each additive to be tested to separate samples of a fuel oil mixture containing 50 percent by volume of a straight run No. 2 fuel oil distillate and 50 percent by volume of a catalytically cracked fuel oil distillate.

The stability test referred to above was carried out on the mixed fuel oil compositions by heating 600 gram samples of the fuel oil compositions for a period of 16 hours at 210 F. in loosely stoppered, one-quart clear glass bottles. Following the heating period each test sample was cooled to room temperature and filtered by suction through a tared, medium porosity fritted glass Gooch-type crucible. The sludge in each crucible was washed with heptane. Complete removal of the sludge adhering to'the inside of the bottles was obtained by means of a 'rubberpoliceman and heptane. The respec tive crucibles were dried in an oven maintained at 210 F. for 1 hour, cooled in a desiccator and reweighed. The increase in weight was recorded as milligrams of sludge per 600 grams of oil.

The fuel oil mixtures referred to as Blends A and B in the following table were 1:1 by volume mixtures of Eastern Venezuela straight run and fluid catalytically cracked No. 2 fuel oil distillates. Blend A had the following properties:

Gravity, API 28.7 Specific gravity (607160 F.) 0.8833 Viscosity, SUS at 100 F. 35.6 Color, NPA 2-- Pour point, F. 0 Flash point, O.C., F 180 Neutralization value, acid No. 0.05 Distillation:

Initial boiling point, F. 385 End'boiling point, F; 642 Bromine No f 'f 16.5 Qlefins, wtjpercent ."...'...t 223 6 Aromatics, vol. percent; 262 Aniline point, F. 4,1 6, Ash, oxide, wt. percent (0.01

The foregoing values are similarto, and are considered typical of, those for the corresponding properties of Blend B, also referred to inthe table.

The 3-tallow-aminopropylamine referred to in the table was a mixture of S-fattyalkyland alkenylaminopropylamines containing approximately percent active ingredient and had "a theoretical molecular weight of 320, a combining weight of approximately .400 and a melting range of approximately 44 to 48 C. The fatty alkyl and alkenyl-substituents of the diamine' were derived from animal tallow fatty acids. Accordingly, the 3 tallo aminopropylamine contained. predominantly 3-oleylaminopropylamine together with substantial-but lesser proportions of 3-octadecyland 3-hexadecylaminopropyl amines, and small amounts of 3myristyl--;and 3 linoleylaminopropylamines. The 2,4 dinaphthenyl 3 thiaglutaric acids employed in making the salts in thefollow ingtable were prepared from petroleum naphthenic acids and had a neutral equivalent of 298, a sulfur contentof 3.24 percent, and a calculated molecular weight of 596 Table A Sludge, Mg./600 Fuel Oil Composition G. 011

' After 16 Hrs.

1. Blend A50l50 Mixture of E.V.S.R. and F.0.0. No. 2

Fuel Oil Distillate 18.2 2. Blend A plus 0.05 Wt. percent 3Tallow"-ammoniumpropylamrnonium-Z.4-Diuaphthenyl-3-Thiaglutarate (1:1 Mol Ratio 5.1 3. Blend A plus 0.05 Wt. percent of Dl-(3Aminopropyl- Tallow" -a.mmonium) -2,4-Dinaphthenyl -3 -lhiaglutarate (2:1 Mol Ratio). e 3.1 4. Blend B-50/50 Mixture of E.V.S.R. and F.O.C. No. 2

Fuel Oil Distillate 31.8 5. Blend B plus 0.02 Wt. percent of Ethylene Diamine Mono- Petroleum Naphthenate 315.0 6. Blend B plus 0.02 Wt. percent of Ethylene Diamine Di- Petroleum Nanhtheflate 34. 8

Compositions 2 and 3 in the foregoing table are spe cific embodiments of the invention. The results shown in the table for these compositions are considered typical} of those obtainable with the 2,4-dinaphthenyl-3 thiaglutarate addition salts of this invention. Comparison of the results obtained for compositions 2 and 3 with those obtained for blank composition 1 clearly indicates the marked improvement in sludging characteristics .ofmixed distillate fuel oils that is obtainable with the salts included by this invention. Comparison of the results obtained for compositions 5 and 6 with those obtained for composition 4 in the foregoing table indicates that the results obtained by the salts of this invention are not: typical of those obtained by diamine salts of carboxylic acids in general.

'The utility of the herein disclosed salts has been further demonstrated by subjecting other liquid distillatepe; troleum fuels to stability tests. For example, compositions comprising thermally cracked gasoline distillate and salts of this invention have been subjected to the standard oxidation stability test ASTM D525-49. According to this test, the gasoline sample is introduced into an oxidation bomb and oxygen is added to a pressure of about lp.s.i. The charged bomb is placed in a boiling water' bath and the gas pressure in the bomb is recorded. The end of the induction period, i.e., the point at which rapid absorption of the oxygen by the gasoline takes place, is the time when a sharp drop in pressure (at least 2 p.s'.i. in 15 minutes) f The results obtained by the foregoing-tests are prein-TableBbelow:

i '2 V Table 3 Additive Concentration 7 Tndrmtimi V Period Compositions 3 and 4 in Table B are specific embodiments of the invention. Comparison of the induction periods for these compositions with those for gasoline composition 2 (inhibited with a standard commercial inhibitor) and for uninhibited gasoline composition 1 indicates the improvement obtainable by the salts of this invention.

It will be understood that the foregoing embodiments of the invention are merely illustrative and that other members of the class of sludge inhibiting salts included by the invention can be substituted therein in the same or equivalent concentrations within the herein disclosed rangesto prepare distillate fuel compositions having similarly improved stability characteristics. Specific examples of other salts that are suitable for the purposes of this invention and which can be used in lieu of those in the above-indicated embodiments are the substantially neutral diammonium salts and the diamino-diammonium salts of 3-lauryl-, 3-octadecyl-, 3-octadecenyl-, and 3- octadecadienylaminopropylamines and 2,4-ldi-petroleum naphthenyl 3 thiaglutaric acid, 2,4 di cyclopenttyl- 3-thiaglutaric acid, 2,4-di-cyclohexyl-3-thia glutaric acid and 2,4-di cyclohexylhexadecyl-3-thiaglutaric acid.

If desired, the stable distillate fuel compositions of this invention may contain, in addition to the additives disclosed herein, other improvement agents. For example, fuel; oil compositions may contain additionally oxidation inhibitors, flash point control agents, corrosion inhibitors, anti-foam agents, ignition quality improvers, combustion improvers and other additives adapted to improve the oils in one or more respects. Gasoline compositions may contain additionally anti-knock agents, corrosion inhibitors, dyes,-color inhibitors, ignition control additives, and other conventional additives.

It Will be apparent to those skilled in the art that many variations of the invention may be resorted to without departin from the spirit thereof. Accordingly, only such limitations should be imposed as are indicated in the claims appended hereto.

is a division of application Serial No. 449,492, filed August '12, 195'4,now US. Patent 'No. 2,899,459.

We claim: 1. A liquid petroleum distillate fuel composition that is normally unstable during storage comprising a major propor tionof the liquid petroleum distillate fuel and a small amount of a salt of a 2,4-dinaphthenyl-3-thiaglutaric acid and a 1,-3 diaminopropane having the general formula:

where -R'is an aliphatic radical containing from, 8 to 30 carbon :atoms, the molecular ratio of said acid and said l,3,-diaminopropane in said salt being about 1:1 to 1:2, said small amount being sufiicient to improve the storage stability of the distillate .lfuel. A gasoline composition tending to formgum during storage comprising a major proportionof a petroleum dis '8 tillate 'rfuel boiling "in the gasoline range and a small; amount of a salt f of a '2,4-dinaphthenyl 3 thiaglutaric acid and a 1,3-diaminopropane having the general formula! T A iiit-oHr-oHi-ctn-NH; I where R is an aliphatic radical containing from 8 to 30 carbon atoms, the molecular ratio ofsaid acid and said 1,3-diaminopropane insaid salt being about 1:1 to 1:2, said small amount being sufiicient to inhibit gum formation in the gasoline. V

3. A fuel oil composition comprising a major proportion of a distillate fueloil tending to depositsludge and a small amount of a salt of a 2,4-dinaphthenyl-3-thiaglutaric acid and a 1,3-diaminopropane having the general formula:

R HhT-CHr-CHr-CHz-NH, where R is an aliphatic radical containing'from 8 to 30 carbon atoms, the molecular ratio of said acid and said 1,3-diaminopropane in said salt being about 1:1 to 1:2, said small amount being sufiicient to inhibit sludge deposition from said oil. 7

4. A -fuel oil composition comprising a major proportion of a mixture of straight run and catalytically cracked distillate fuel oils 't'ending'to deposit sludge and containing a small amount of a salt of 2,4-dinap'hthenyl-3 -triaglutaric acid and a 1,3-diaminopr'op'ane having the general 'formula:

R H1 I -CH2-CH2- CH2NH2 where R is'an aliphatic radical containing from 8 to 30 carbon atoms, the molecular ratio of said acid and said 1,3-diaminopropane in said salt being about 1:1 to 1:2, said small amount being sufiicient to inhibit sludge deposition from said mixture of oils.

5. The composition of claim 4 wherein said small amount is between about 0.005 and about 1.0 percent by weight of said mixture of oils.

6. A fuel oil composition comprising a major proportion of a mixture of straight run and catalytical-ly cracked distillate --fuel oils tending to deposit sludge and containing a small amount of a salt of (a) a 2,4-dinaphthenyl-3 thiaglutaric acid whose naphthenyl substituents are derived from petroleum 'naphthenic acids, and ('b) a 1,3diaminopropane selected from thetgroup consisting of 3-alkyland 3-alkenyl-aminopropylamines wherein the alkyl and a1- kenyl substituents contain from 12 to 18 carbon atoms,- the molecular ratio of said acid and said 1,3-diaminopropane in said salt being about 1: 1 to .1 :2, said small amount being sufiicient to inhibit sludge deposition from said mixture of oils.

7. A fuel oil composition comprising a major proportion of a mixture of straight run and catalytically crackeddistillate fuel oils tending to deposit sludge and containing a small amount of a substantially neutral .diamrnonium salt of (a) a 2,4-dinaphthenyl-3-thiaglutaric acid whose naphthenyl substituents are derived from petroleum naphthenic acids, and (b') mixed 3-alkyland 3-alkenylaniinopnopylamines wherein said alkyl and alkenyl substituents contain from 14 to 18 carbon atoms, said small amount being sufiicient to inhibit sludge deposition from saidmixtureof oils.

=8. A fuel oil composition comprising a major proportion of a mixture of straight run and catalytically-cracked distillate fuel oils tending to deposit sludge-and cont'a'ining a small amount of a substantially neutral dia'rn'n'io-v nium salt of '(a') a 2,4-dinaphthenyl-3-tliiaglutaric acid Whose naphthenyl substituents are derived from petroleum naphthenic acids, and (b) .3-oleylaminopropylamine, said small amount bein sufiicient to inhibit sludge :depos'it'ion from said'mixtureof'oils.

9; A fuel oil" composition comprising a major, .propprg tionof a'mixtureof'straight runaud catalytica'lly cracked distillate fuel oils tending to deposit sludge and containing a small amount of a diamino-diammonium salt of (a) a 2,4-dinaphth'enyl-3-thiaglutaric acid whose naphthenyl substituents are derived from petroleum naphthenic acids, and ([2) mixed 3-alkyland 3-alkeny-1aminopropylamines wherein said alkyl and alkenyl substituents contain from 14 to 18 carbon atoms, said small amount being sufiicient to inhibit sludge deposition from said mixture of oils.

10. A fuel oil composition comprising a major pro- 1 portion of a mixture of straight run and catalytically cracked distillate fuel oils tending to deposit sludge and 10 containing a small amount of a diamino-diammonium salt of (a) a 2,4-dinaphthenyl-3-thiaglutaric acid Whose naphthenyl substituents are derived from petroleum naphthenic acids, and (b) 3-oleylaminopropylamine, said small amount being suflicient to inhibit sludge deposition from said mixture of oils.

References Cited in the file of this patent UNITED STATES PATENTS 2,868,628 Chenicek Jan. 13, 1959 

1. A LIQUID PETROLEUM DISTILLATE FUEL COMPOSITION THAT IS NORMALLY UNSTABLE DURING STORAGE COMPRISING A MAJOR PROPORTION OF THE LIQUID PETROLEUM DISTILLATE FUEL AND A SMALL AMOUNT OF A SALT OF A 2,4-DINAPHTHENYL-3-THIAGLUTARIC ACID AND A 1,3-DIAMINOPROPANE HAVING THE GENERAL FORMULA: 